Probing structural changes of a molecule induced by charge transfer is important for understanding the physicochemical properties of molecules and developing new electronic devices. Here, we interrogate the structural changes of a single diketopyrrolopyrrole (DPP) molecule induced by charge transport at a high bias using scanning tunneling microscope break junction (STM-BJ) techniques. Specifically, we demonstrate that application of a high bias increases the average nonresonant conductance of single Au-DPP-Au junctions. We infer from the increased conductance that resonant charge transport induces planarization of the molecular backbone. We further show that this conformational planarization is assisted by thermally activated junction reorganization. The planarization only occurs under specific electronic conditions, which we rationalize by ab initio calculations. These results emphasize the need for a comprehensive view of single-molecule junctions which includes both the electronic properties and structure of the molecules and the electrodes when designing electrically driven single-molecule motors.

We study the single-molecule transport properties of small bandgap diketopyrrolopyrrole oligomers (DPPn, n = 1-4) with lengths varying from 1 to 5 nm. At a low bias voltage, the conductance decays exponentially as a function of length indicative of nonresonant transport. However, at a high bias voltage, we observe a remarkably high conductance close to 10(-2) Go with currents reaching over 0.1 mu A across all four oligomers. These unique transport properties, together with density functional theory-based transport calculations, suggest a mechanism of resonant transport across the highly delocalized DPP backbones in the high bias regime. This study thus demonstrates the unique properties of diketopyrrolopyrrole derivatives in achieving highly efficient long-range charge transport in single molecule devices.

Charge transport by tunnelling is one of the most ubiquitous elementary processes in nature. Small structural changes in a molecular junction can lead to significant difference in the single-molecule electronic properties, offering a tremendous opportunity to examine a reaction on the single-molecule scale by monitoring the conductance changes. Here, we explore the potential of the single-molecule break junction technique in the detection of photo-thermal reaction processes of a photochromic dihydroazulene/vinylheptafulvene system. Statistical analysis of the break junction experiments provides a quantitative approach for probing the reaction kinetics and reversibility, including the occurrence of isomerization during the reaction. The product ratios observed when switching the system in the junction does not follow those observed in solution studies (both experiment and theory), suggesting that the junction environment was perturbing the process significantly. This study opens the possibility of using nano-structured environments like molecular junctions to tailor product ratios in chemical reactions.

Even though five-membered rings, for example, thiophene, are ubiquitous in organic and molecular electronics, as a class of molecules, they resist a simple interpretation. Generally containing four sp(2)-hybridized carbon atoms, the fifth position can be filled by any number of substituents. This flexibility leads to a diverse range of electronic properties, but also presents a challenge for deriving a model description. Starting from a noninteracting Hamiltonian obtained from Kohn-Sham density functional theory calculations, we derive an effective four-site model that provides a unified description of these systems. We rationalize the zero-bias conductance of these molecules in terms of aromaticity and connectivity. The conductance was found to be highly sensitive to connectivity, as for benzene, but we also found the conductance to be sensitive to aromaticity. The model predicts the same relative conductance as reported in prior experiments in almost all cases and provides a link between chemical intuition and single-molecule conductance. The method used to develop the model is general and could be applied to other types of molecules.

Quantum interference effects, whether constructive or destructive, are key to predicting and understanding the electrical conductance of single molecules. Here, through theory and experiment, we investigate a family of benzene-like molecules that exhibit both constructive and destructive interference effects arising due to more than one contact between the molecule and each electrode. In particular, we demonstrate that the π-system of meta-coupled benzene can exhibit constructive interference and its para-coupled analog can exhibit destructive interference, and vice versa, depending on the specific through-space interactions. As a peculiarity, this allows a meta-coupled benzene molecule to exhibit higher conductance than a para-coupled benzene. Our results provide design principles for molecular electronic components with high sensitivity to through-space interactions and demonstrate that increasing the number of contacts between the molecule and electrodes can both increase and decrease the conductance.

Single molecule conductance measurements are often interpreted through computational modeling, but the complexity of these calculations makes it difficult to directly link them to simpler concepts and models. Previous work has attempted to make this connection using maximally localized Wannier functions and symmetry adapted basis sets, but their use can be ambiguous and non-trivial. Starting from a Hamiltonian and overlap matrix written in a hydrogen-like basis set, we demonstrate a simple approach to obtain a new basis set that is chemically more intuitive and allows interpretation in terms of simple concepts and models. By diagonalizing the Hamiltonians corresponding to each atom in the molecule, we obtain a basis set that can be partitioned into pseudo-σ and -π and allows partitioning of the Landuaer-Büttiker transmission as well as create simple Hückel models that reproduce the key features of the full calculation. This method provides a link between complex calculations and simple concepts and models to provide intuition or extract parameters for more complex model systems.

Guidelines to predict trends in the electrical conductance of molecules have been developed for the π-system of conjugated systems. Little is known, however, about the conductance of the underlying σ-systems because the π-system usually dominates the transport. Here we study a family of bipyridine-based molecules using STM-break junction experiments and density functional theory transport calculations. We use different lengths and substitution patterns to probe the role of both the σ-system and the π-system in controlling conductance. By exploiting the destructive interference feature found in the π-system of the meta-coupled six-membered aromatic rings, we show that the conductance of the σ-system of a meta-coupled molecule can be probed directly and can even exceed that of its para-coupled analog. These results add to the understanding of the conductance through the chemically hidden σ-electrons.

Quantum interference, be it destructive or constructive, has a substantial influence on the magnitude of molecular conductance and consequently there is significant interest in predicting these effects. It is commonly thought that cross-conjugated paths result in suppressed conductance due to destructive quantum interference. Using H\"uckel theory and DFT calculations we investigate systems that break this cross-conjugation rule of thumb. We predict and rationalize how a class of conjugated molecules containing closed loops can exhibit destructive interference despite being linearly conjugated and exhibit constructive interference despite being cross-conjugated. The arguments build on the graphical rules derived by Markussen et al. [1] and the hitherto neglected effects of closed loops in the molecular structure. Finally, we identify the 1,3 connected Azulene molecule as belonging to the closed-loop class and argue that this explains recent measurements of its electrical conductance.

The triazatriangulene (TATA) ring system was investigated as a binding group for tunnel junctions of molecular wires on gold surfaces. Self-assembled monolayers (SAMs) of TATA platforms with three different lengths of phenylene wires were fabricated, and their electrical conductance was recorded by both conducting probe-atomic force microscopy (CP-AFM) and scanning tunneling microscopy (STM). Similar measurements were performed for phenylene SAMs with thiol anchoring groups as references. It was found that, despite the presence of a sp(3) hybridized carbon atom in the conduction path, the TATA platform displays a contact resistance only slightly larger than the thiols. This surprising finding has not been reported before and was analyzed by theoretical computations of the transmission functions of the TATA anchored molecular wires. The relatively low contact resistance of the TATA platform along with its high stability and directionality make this binding group very attractive for molecular electronic measurements and devices.